Inspired by the sophisticated and powerful machinery of enzymes, we aim to use the tools of supramolecular chemistry (reversible and weak-interaction driven recognition) to address open challenges in catalysis, organic synthesis and bioinorganic chemistry.
Supramolecular recognition accelerates reactions by bringing the reactive functions in proximity and controls all types of selectivity (site-, chemo- and stereo-selectivity) via preorganization of the substrate towards the reactive site. We apply these concepts to address open problems in organic chemistry, from controlling radical reactions such as the HAT functionalization of aliphatic C-H bonds, to facilitating difficult macrocylizations.
We designed supramolecular iron and manganese catalysts, competent for challenging C-H oxidation reactions, equipped with crown ether receptors to bind and orient protonated primary amines. Substrate binding enables preorganization and unlocks selective oxidation of remote (C8 and C9) C-H bonds, with a selectivity predictable by NMR analysis. Ammonium recognition also allows the replicatin of elusive enzymatic features inaccessible with conventional catalysts.
This project is a collaboration with Prof. Miquel Costas at the university of Girona (Catalonia, Spain) and Prof. Stefano Di Stefan at La Sapienza university of Rome (Italy).
Representative publications
Proximity Effects on the Reactivity of a Nonheme Iron (IV) Oxo Complex in C-H Oxidation
A. Fagnano, F. Frateloreto, R. Paoloni, C. Sappino, O. Lanzalunga, M. Costas,* S. Di Stefano,* G. Olivo,* Angew. Chem. Int. Ed. 2024, 63, e202401694.
L. Vicens, G. Olivo*, M. Costas*, Angew. Chem. Int. Ed. 2022, 61, e202114932
Predictable Selectivity in Remote C−H Oxidation of Steroids: Analysis of Substrate Binding Mode
G. Olivo*,¶ G. Capocasa,¶ B. Ticconi, O. Lanzalunga, S. Di Stefano*, M. Costas*, Angew. Chem. Int. Ed. 2020, 59, 12703-12708
G. Olivo*, G. Farinelli, A. Barbieri, O. Lanzalunga, S. Di Stefano*, M. Costas*, Angew. Chem. Int. Ed., 2017, 56, 16347-16351.
Nanoconfinement of organic molecules alters their innate reactivity by enforcing peculiar conformations and stabilizing high-energy intermediates. We use of self-assembled organic capsules to recognize organic molecules and alter their innate reactivity, for instance by accelerating the challenging closure of medium and large sized rings.
Representative publications
E. Spatola, R. Cacciapaglia,* F. Frateloreto, A. Procopio, F. Giannetti, L. Napoli, M. De Angelis, S. Di Stefano,* G. Olivo* Org. Lett. 2025, 27, 6605-6610